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Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol
Analytica Chimica Acta xxx (xxxx) xxx
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Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol Duanduan Yin, Jian Liu, Xiangjie Bo**, Liping Guo* Key Laboratory of Nanobiosensing and Nanobioanalysis at Universities of Jilin Province, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, PR China
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
A facile and simple synthetic method of 3D CoFe2Se4/PCF via electrospinning for the first time. The CoFe2Se4/PCF shows high electrocatalytic activity to dihydroxybenzene isomers oxidation. Simultaneous detection of trace of hydroquinone, catechol and resorcinol. Obtained a wide linear range and low detection limits.
a r t i c l e i n f o
a b s t r a c t
Article history: Received 19 July 2019 Received in revised form 21 September 2019 Accepted 24 September 2019 Available online xxx
In this study, cobalt-iron selenides embedded in porous carbon nanofibers (CoFe2Se4/PCF), derived from Prussian blue analogues, was prepared as a novel phenolic sensor. The obtained CoFe2Se4/PCF nanocomposites show three-dimensional (3D) networks nanostructures that can supply a desirable conductive network to accelerate electron transfer and avoid the aggregation of CoFe2Se4 nanoparticles. Electrochemical detection of hydroquinone (HQ), catechol (CC) and resorcinol (RS), at CoFe2Se4/PCF modified glassy carbon electrode (GCE) were researched. The results show the obtained 3D CoFe2Se4/ PCF/GCE exhibits excellent electrochemical properties towards the simultaneous testing trace of HQ, CC and RS. The obtained electrode provides wide linear ranges of 0.5e200, 0.5e190 and 5e350 mM and low detection limit of 0.13, 0.15 and 1.36 mM for HQ, CC and RS, respectively. The as-prepared phenolic sensor displays satisfied selectivity and long-term storage stability. In addition, the constructed sensor can be used to determine HQ, CC and RS in actual samples. © 2019 Elsevier B.V. All rights reserved.
Keywords: Phenolic sensor CoFe2Se4/PCF nanocomposites Simultaneous testing Electrocatalysis
1. Introduction
* Corresponding author. ** Corresponding author. E-mail addresses: [email protected] (X. Bo), [email protected] (L. Guo).
Hydroquinone (HQ), catechol (CC) and resorcinol (RS), as three isomers of dihydroxybenzene, have been widely used in production of antioxidant, developer, medicines, pesticides, dye, cosmetics, tanning and photostabilizer [1e4]. However, dihydroxybenzene is poisonous and hard to degrade, menacing the environment and
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Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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crippling human and animal health [5,6]. It’s high time for researchers to develop an analytical technique that is sensitive and fast to detect dihydroxybenzene. So far, various analytical methods have been used to determine dihydroxybenzene isomers, including electrochemical methods [7], fluorescence [1], spectrophotometry [8], chemiluminescence [9], high performance liquid chromatography [10], capillary electrochromatography [11] and gas chromatography/mass spectrometry [12], Among these methods, electrochemical method has been attracted wide attention owing to its advantages of convenient operation, timesaving, low production cost and high sensitivity. Unfortunately, the dihydroxybenzene isomers, especially the oxidation and reduction of HQ and CC, are usually overlapped at ordinary electrode owing to their similar stereochemical structure. Therefore, it is almost impossible to detect them on bare GCE at the same time. In order to solve this issue, various materials are used to modify electrodes to detect HQ and CC, such as 3D sulfur/nitrogen co-doped graphene, Cu-MOF199/single-walled carbon nanotubes, multiwalled carbon nanotubes/polydopamine/gold nanoparticles composites and sodium citrate-derived 3D interconnected porous carbon modified GCEs [13e16]. Nevertheless, there are a few papers that report the sensitive and rapid detection of three dihydroxybenzene isomers. Therefore, the design of an advanced material with good catalytic activity to detect three dihydroxybenzene isomers is key to construct a sensitive phenolic biosensor. Metal selenides, have been received wide attention recently due to their excellent physical and electrochemical properties [17e19]. Among many metal selenides MSex (M ¼ Mo, Fe, Co, Mn Cu and Ni), FeSe2 and CoSe2 are attracting attention owning to their excellent electrical conductivity, substantial electrocatalytic activity and high specific capacitance, etc., [20,21]. In addition, catalysts with bimetallic active sites have better selectivity and catalytic activity in different chemical conversion processes than single metal catalysts,
which is due to the bonding among different metals could set up inherent polarity [22,23]. Therefore, CoFe2Se4 can be considered as the electrode material for an electrochemical sensor. However, semiconducting CoFe2Se4 has low density of available active sites and conductivity, limiting their use in electrocatalytic applications. Hence, developing more effective material as support to maximize exposure of the electrocatalytically active centre of CoFe2Se4 to substrates is necessary. Porous carbon fibers (PCF) with their ability to be woven into interconnected three-dimensional (3D) network structures have attracted attention, which can accelerate the transfer transport of materials and electrons [24]. PCFs have been widely used as supporting substrates in field of catalysis. Highly porous structure and high electrical conductivity make PCF an excellent supporting material for CoFe2Se4. Thus, we expect that CoFe2Se4/PCF nanocomposites will demonstrate excellent electrocatalytical properties because of their synergies. Herein, we developed a new electrocatalyst by selenizing the poly(acrylonitrile) (PAN) nanofibers embedded with nanocrystals of cobalt iron-based prussian blue analogues (CoFe-PBA) and CaCO3. After acid treatment, the CoFe2Se4 encapsulated into PCF (CoFe2Se4/PCF) were obtained. The specific steps are shown in Scheme 1. The results indicate that the 3D CoFe2Se4/PCF nanocomposites exhibit outstanding electrocatalytical properties while simultaneous testing of trace HQ, CC and RS. 2. Experimental 2.1. Reagents and instruments Hydroquinone (HQ), catechol (CC), and resorcinol (RS) were purchased from Tianjin, China. Bisphenol A, lysine, urea acid (UA) and ascorbic acid (AA) were obtained from Sinopharm Chemical
Scheme 1. Illustration of the preparation of CoFe2Se4/PCF.
Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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Reagent Co., Ltd. Polyacrylonitrile (PAN, average MW 80000), dimethylformamide (DMF, 99.5%), selenium powder, calcium carbonate (CaCO3, 99%), Nafion (5 wt %), hydrochloric acid (HCl, 37%), ethanol (C2H5OH, 99%) and potassium hydroxide (KOH, 99%) were obtained from Sigma-Aldrich. Cobalt chloride (CoCl26H2O, 99%), sodium citrate (Na3C6H5O72H2O, 98%) glucose and potassium ferricyanide (K3[Fe(CN)6], 99.5%) were purchased from Aladdin Reagent Company. All other chemicals were analytical grade and used without further purification. All electrochemical experiments were carried out on a CHI 660C Electrochemical Workstation (CH Instruments, China) in a conventional three-electrode configuration. The modified glassy carbon electrode (GCE, 3 mm diameter), platinum electrode and Ag/AgCl (in saturated KCl solution) electrode work as the working electrode, the counter electrode and the reference electrode, respectively. All potentials in this paper involved versus Ag/AgCl. X-ray diffraction (XRD) patterns were acquired with an X-ray D/max-2200vpc (Rigaku Corporation, Japan) instrument operated at 40 kV and 20 mA using Cu Ka radiation (l ¼ 0.1541 nm). SEM images and EDX were acquired on a HITACHI SU8010 SEM. Nitrogen adsorptionedesorption isotherms were measured on an ASAP 2020 Micromeritics (USA) at 77 K. The BET method was utilized to calculate the specific surface area. The pore size distribution plot was derived from the adsorption branch by using the BJH model. 2.2. Synthesis of CoFe-PBA CoFe-PBA was synthesized as reported previously with some modification [25]. The details are listed in Supporting information. 2.3. Synthesis of PAN/CoFe-PBA/CaCO3 nanofibers and CoFe2Se4/PCF CoFe-PBA (0.8 g), polyacrylonitrile (PAN, 0.8 g, average MW 80000) and CaCO3 (0.4 g) were dispersed in N, N-dimethylformamide (DMF). Subsequently, the solution was stirred overnight and then poured into a syringe. Afterward, a high pressure of 13 kV was applied and the collector was placed 15 cm from the spinneret for obtaining PAN/CoFe-PBA/CaCO3 fiber. Furthermore, the nanofibers were dried at 60 C for 24 h in vacuum condition, which is benefit for forming stable network structures after the remove of solvent residues. Subsequently, the PAN/CoFe-PBA/CaCO3 nanofibers and selenium powder (1 g) were put into a tube furnace. In addition, the distance between the selenium powder and the nanofibers was 0.5 cm. Then the tube furnace was place at the downstream side. Firstly, the PAN/CoFe-PBA/CaCO3 nanofibers were pre-treated in nitrogen at 270 C at a heating rate of 1 C min1 for 1 h. Then, they were pyrolyzed at 500 C at a heating rate of 5 C min1 for 2 h. Afterward, the obtained nanofibers were removed CaCO3 by immersing into 1.0 M HCl. After washing and drying for 24 h at 60 C in vacuum, the final CoFe2Se4/PCF-2 sample was then obtained. In addition, CoFe2Se4/PCF-1 and CoFe2Se4/PCF-3 samples were prepared through putting 0.4 mg and 1.6 mg of CoFe-PBA into the spinning solution, respectively. In comparison, CoFe2Se4 catalyst was synthesized by pyrolyzing directly CoFe-PBA at the same condition. In addition, PCF catalyst was also prepared by calcining PAN/CaCO3 under identical condition and further acid treatment. 2.4. Preparation of the modified electrodes To begin with, GCE was polished by alumina powders prior to modification, then cleaned thoroughly with deionized water. The clean GCE was dried in air. Then, 3 mg of catalyst was dispersed in
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1 mL Nafion (0.5 wt %) and treated by sonicate for 0.5 h to form the catalyst suspension. Next, 5 mL of the suspension was casted on the surface of GCE and dried in air. 3. Results and discussion 3.1. Characterization of CoFe2Se4/PCF-2 composites The phase of CoFe-PBA is investigated by XRD in Fig. S1. The sharp diffraction peaks confirm CoFe-PBA has been prepared successfully [26]. Fig. 1A displays the XRD patterns of CoFe2Se4/PCF-2. The four characteristic peaks at 33.47, 44.90 , 51.52 and 70.48 correspond to the (112), (114), (020) and (404) planes of the CoFe2Se4 (JCPDS No. 65e2337), respectively [27]. In addition, a broad 25 peak at CoFe2Se4/PCF-2 sample can be assigned to (002) plane of graphitic carbon, suggesting that CoFe2Se4/PCF-2 catalyst has been successfully synthesized. As shown in Fig. 1B, CoFe-PBA has cubic shape and relatively uniform size of 250e500 nm. After calcination, the agglomeration of CoFe-PBA takes place obviously (Fig. 1C). The morphology of CoFe-PBA, CaCO3 and PAN after electrospinning (PAN/CoFe-PBA/CaCO3 nanofibers) are presented in Fig. 1D. Compared to PAN nanofibers (Fig. S2A), there are obvious protuberances on the surface of PAN/CoFe-PBA/CaCO3 nanofibers due to successful introduction of CoFe-PBA and CaCO3. In particular, a plurality of nanofibers is winded to construct a three-dimensional network. Fig. 1E exhibits the morphologies of PAN/CoFe-PBA/CaCO3 after the pyrolysis treatment. The surface of the selenized fibers of PAN/CoFe-PBA/CaCO3 have two different sizes of protrusions, corresponding to CaCO3 (Fig. S2B) and CoFe-PBA, respectively. After acid treatment (Fig. 1F), CoFe2Se4/PCF catalyst with porous and 3D net-like structures was obtained. EDX spectrum has been applied to further reveal the chemical composition of the CoFe2Se4/PCF-2. Fig. 1G displays the existence of C, N, O, Co, Fe and Se in CoFe2Se4/ PCF-2. The N2 adsorption-desorption isotherms, BET specific surface area and pore volume of CoFe2Se4/PCF-2 and CoFe2Se4 are presented in Fig. S3 and Table S1, the data indicating PCF can increase the BET specific surface area and pore volume of CoFe2Se4, which is advantageous to higher electrocatalytic activity by offering more active sites. 3.2. Electrocatalytic oxidation of HQ, CC and RS at CoFe2Se4/PCF-2 To explore the electrocatalytic activity of CoFe2Se4/PCF to HQ, CC and RS oxidation, cyclic voltammetry (CV) was employed. Fig. 2(AC) shows the CVs at bare GCE, PCF/GCE, CoFe2Se4/GCE and CoFe2Se4/PCF-2/GCE in 0.1 M PBS (pH 7.0) containing 0.2 mM HQ, CC and RS, respectively. Fig. 2A displays a pair of broad redox peaks with small peak currents when bare GCE is used to detect HQ, which is similar to that of CoFe2Se4/GCE. When PCF/GCE is used to detect HQ, the redox peaks are not evident although the background currents increase obviously. In contrast, CoFe2Se4/PCF-2/ GCE reveals a pair of significant redox peaks. It can be seen that the current of oxidation peak for the CoFe2Se4/PCF-2/GCE (Ipa ¼ 11.78 mA) is about 5.8 times higher than that of CoFe2Se4/GCE (Ipa ¼ 2.04 mA). Therefore, CoFe2Se4/PCF-2/GCE exhibits much better electrocatalytic activity than GCE, PCF/GCE and CoFe2Se4/GCE to HQ. Fig. 2B displays the redox peaks of CC on different electrodes, which are similar to that of HQ. Nevertheless, only one oxidation peak of RS on the various electrodes is gained (Fig. 2C), indicating the oxidation of RS is a completely irreversible. Fig. 2D reveals the CVs at bare GCE, PCF/GCE, CoFe2Se4/GCE and CoFe2Se4/PCF-2/GCE in 0.1 M PBS (pH 7.0) mixture solution containing 0.2 mM HQ, CC and RS. The oxidation and reduction peaks of HQ and CC are overlapped on bare GCE. Furthermore, the peak of HQ, CC and RS is hardly observed on PCF/GCE. Hence, it is infeasibility to detect
Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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Fig. 1. (A) XRD pattern of CoFe2Se4/PCF. SEM images of CoFe-PBA (B), CoFe2Se4 (C), PAN/CoFe-PBA/CaCO3 nanofibers (D), CoFe2Se4/PCF precursor (E) and CoFe2Se4/PCF sample (F). (G) EDX spectrum of CoFe2Se4/PCF.
simultaneously HQ, CC and RS at bare GCE and PCF/GCE. For CoFe2Se4/GCE, the peak currents are small though the redox peaks of HQ and CC and the peak of oxidation of RS are provided. As expected, the two pairs of redox peaks at 0.102 V, 0.048 V (HQ) and 0.212 V, 0.172 V (CC) and one oxidation peak at 0.589 V (RS) are found in the CVs for CoFe2Se4/PCF-2/GCE. The two pairs of redox peak currents of HQ and CC and the oxidation peak current of RS at CoFe2Se4/PCF-2/GCE are higher than those of CoFe2Se4/GCE. From the results above, the simultaneous detection of HQ, CC and RS can be gained on CoFe2Se4/PCF-2/GCE. The excellent performance may be explained the following reasons. To begin with, 3D interconnected structure PCF with continuous path is advantageous to accelerate electron transfer. Furthermore, PCF with large surface area is benefit for allowing the facile accessibility of the electrode/ electrolyte interface, leading to a promotion of electrochemical performance to HQ, CC and RS. Finally, PCF could avoid the collapse and aggregation of CoFe-PBA, which is favorable for improving electrocatalytic activity. In addition, the influence of the content of CoFe2Se4 is researched (Fig. 2E). It is shown that CoFe2Se4/PCF-2/ GCE has the best electrocatalytic effect. Therefore, CoFe2Se4/PCF-2/ GCE was selected for subsequent experiments.
3.3. Influence of scan rate and pH Fig. S4 depicts the peak currents of HQ and CC and the peak current of RS have a good linear relationship with the scan rate. Those results indicate that the electrochemical oxidation of HQ, CC
and RS are adsorption-controlled electrochemical processes on the CoFe2Se4/PCF-2/GCE [28]. Afterward, Fig. 3A provides the effect of solution pH (4.0e8.0) on the response of HQ, CC and RS at CoFe2Se4/PCF-2/GCE via differential pulse voltammetry (DPV). The oxidation peak potential of HQ, CC and RS shifts negatively with the increase of pH, revealing that the oxidations of HQ, CC and RS involves protons. Fig. 3B depicts the linear relationship between the oxidation peak potential of HQ, CC and RS. These three lines are nearly parallel, indicating the peak potential difference is a constant. According to the well-known Nernst equation:
dEp 2:303mRT ¼ nF dpH where T is kelvin temperature, R is the universal gas constant, F is the Faraday constant (96485 C mol1), m and n are the number of protons and electrons, respectively. From the slope of dEp/dpH, the value of m/n could be counted to be 1.015, 1.071 and 1.071 to the oxidation process of HQ, CT and RS, respectively. Those results indicate the number of electrons participating is the same as the number of protons of reaction, which is comply with the twoelectron and two-proton process reported previously [13]. Moreover, the oxidation peak currents of HQ, CC and RS reach the largest at the pH 7.0 (Fig. S5). Hence, pH 7.0 is the best pH value for the later study.
Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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Fig. 2. (A)The CVs at bare GCE, PCF/GCE, CoFe2Se4/GCE and CoFe2Se4/PCF-2/GCE in 0.1 M PBS (pH 7.0) containing of 0.2 mM of HQ (A), 0.2 mM of CC (B), 0.2 mM of RS (C) and a mixture of three dihydroxybenzene isomers (each of 0.2 mM) (D). (E) CVs of a mixture of three dihydroxybenzene isomers (each of 0.2 mM) at CoFe2Se4/PCF-x/GCE electrode. Scan rate: 10 mV s-1.
Fig. 3. (A) DPV curves at CoFe2Se4/PCF-2/GCE containing 0.15 mM HQ, 0.15 mM CC and 0.2 mM RS in the pH range from 4.0 to 8.0. (B) The relationship between pH and the oxidation peak potentials of HQ, CC and RS.
3.4. Selective analysis of HQ, CC and RS Quantitative analysis of HQ, CC and RS on CoFe2Se4/PCF-2/GCE are performed by DPV since DPV possesses higher sensitivity than CV. In the case where the concentrations of the other two substances are constant, Fig. 4A, Fig. 4B and Fig. 4C depict the selective detection of HQ, CC and RS. As demonstrated in Fig. 4A and B, HQ is selectively detected in the existence of 50 mM CC and 20 mM RS with obvious response at 0.1 V. The peak currents of HQ increase linearly with the level of HQ while there is no obvious
variation for the currents response of CT and RS are no obvious vary. Inset a displays the liner regression equation and liner range is 0.5e200 mM for HQ. The detection limit (LOD) of HQ is calculated to be 0.13 mM based on a signal-to-noise factor of 3 (S/ N ¼ 3). Similarly, the peak currents of oxidation for CC and RS increase linearly with their concentrations as demonstrated in Fig. 4B, inset b, Fig. 4C and inset c, respectively. The linear ranges for CC and RS are 0.5e190 mM and 5e350 mM with LOD of 0.15 mM and 1.36 mM, respectively. Table 1 displays the comparison of CoFe2Se4/PCF-2/GCE with other catalysts for simultaneous
Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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Fig. 4. (A) DPV of different concentrations of HQ (0.5e200 mM) in the presence of 50 mM CC and 20 mM RS, (B) CC (0.5e190 mM) in the presence of each 50 mM HQ and RS, (C) RS (5e350 mM) in the presence of each 50 mM HQ and CC in 0.1 M PBS (pH 7.0). The corresponding calibration plots between HQ (inset a), CC (inset b) and RS (inset c) concentration and current signal of oxidation peak for CoFe2Se4/PCF-2/GCE, respectively.
Table 1 Comparison of the performances of the simultaneous determination of HQ, CC and RS sensors. Electrode
AuPdNF/rGO/GCE P-rGO/GCE Graphene-CS/GCE UiO-66/MC-3/GCE Cu3(btc)2/CS-ERGO/GCE AgNP/MWCNT/GCE MIL-101(Cr)-rGO-2-CPE aGO1/SPCE CoFe2Se4/PCF-2/GCE
Linear range (mM)
Detection Limit (mM)
Ref.
HQ
CC
RS
HQ
CC
RS
1.6e100 5e90 1e300 0.5e5.0, 5.0e100 5.0e400 2.5e260 10e1400 1e312 0.5e200
2.5e100 5e120 2e400 0.4e100 2.0e200 20e260 4e1000 1e350 0.5e190
2.0e100 5e90 1e550 30e100, 100e400 1.0e200 e e e 5e350
0.5 0.08 0.75 0.056 0.44 0.16 4.1 0.27 0.13
0.8 0.18 0.75 0.072 0.41 0.2 0.66 0.182 0.15
0.7 2.62 0.75 3.51 0.33 e e e 1.36
detection of HQ, CC and RS. The results show the prepared phenolic sensor exhibits a wide linear range and low detection limit, which make the property of the CoFe2Se4/PCF-2/GCE sensor comparable and even better than the reported recently. 3.5. Simultaneous analysis of HQ, CC and RS The excellent property of CoFe2Se4/PCF-2/GCE for HQ, CC and RS detection is also demonstrated via the simultaneously increasing the concentration of three isomers. Three well-separated and distinct oxidation peaks for HQ, CC and RS are represented in Fig. 5A. As shown in Fig. 5BeD, the linear ranges of HQ, CC and RS are 0.5e180 mМ, 1e160 mМ and 10e120 mМ and with LOD of 0.53, 0.84 and 2.62 mM, respectively.
[3] [29] [6] [30] [31] [32] [33] [34] This work
the CoFe2Se4/PCF-2/GCE exhibits satisfactory long-term storage stability.
3.7. Diluted lake water analysis To assess feasibility of CoFe2Se4/PCF-2/GCE, the diluted lake water samples were tested. No target analytes are found in diluted lake water samples. The standard addition method was used to determine HQ, CC and RS. The results are provided in Table 2. The values of recoveries are 95.3e102.0%, 96.9e102.8% and 95.2e100.8% for HQ, CT and RS, respectively. Therefore, the proposed sensor could be used to determine HQ, CC and RS in diluted lake water analysis.
3.6. The selectivity and stability investigated
4. Conclusion
In addition, the selectivity and stability of CoFe2Se4/PCF-2/GCE are also studied. Fig. S6A shows the current responses of CoFe2Se4/ PCF-2 to 0.1 mM HQ, 0.1 mM bisphenol A, 0.1 mM glucose, 0.1 mM lysine, 0.1 mM urea acid (UA) and 0.1 mM ascorbic acid (AA). There is no obvious current change when the interfering substances are added. The selectivity to CC and RS at CoFe2Se4/PCF-2/GCE as shown in Fig. S6B and Fig. S6C, respectively. The results indicating that CoFe2Se4/PCF-2/GCE displays high selectivity at their certain active potentials for HQ, CC and RS. Moreover, the stability of CoFe2Se4/PCF-2/GCE is also investigated. Fig. S6D illustrates that the current signals are lower than 7.13%, 8.34%, 12.18% of the original for HQ, CC and RS after 15 days, respectively, suggesting that
In conclusion, we prepared a novel phenolic sensor based on CoFe2Se4/PCF nanocomposite to determine of trace HQ, CC and RS simultaneously. The as-prepared sensor exhibits excellent electrochemical properties towards the simultaneous testing trace of HQ, CC and RS. The obtained electrode provides wide linear ranges of 0.5e200 mM, 0.5e190 mM and 5e350 mM and low detection limit of 0.13 mM, 0.15 mM and 1.36 mM for HQ, CC and RS, respectively. At the meantime, the obtained sensor provids good antiinterference property and outstanding stability. Moreover, this work opens up the possibility of using three-dimensional PCF loaded metal selenides as a sensing platform for the detection of HQ, CC and RS.
Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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Fig. 5. (A) DPV of different concentrations of HQ (0.5e180 mM), CC (1e160 mM) and RS (10e120 mM) in 0.1 M PBS (pH 7.0). The corresponding calibration plots between HQ (B), CC (C) and RS (D) concentration and current signal of oxidation peak for CoFe2Se4/PCF-2/GCE, respectively.
Table 2 Determination of dihydroxybenzene isomers in lake water samples at the CoFe2Se4/ PCF-2/GCE (n ¼ 3). Sample
1 2 3
Added (mM)
Found (mM)
Recovery (%)
HQ
CC
RS
HQ
CC
RS
HQ
CC
RS
30 60 90
30 60 90
60 120 180
30.6 57.2 88.1
28.1 61.7 87.2
57.5 118.6 181.4
102.0 95.3 97.9
97.0 102.8 96.9
95.2 98.8 100.8
Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments Financial support from National Natural Science Foundation of China (21575021) is highly appreciated.
Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.aca.2019.09.057.
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Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol Duanduan Yin, Jian Liu, Xiangjie Bo**, Liping Guo* Key Laboratory of Nanobiosensing and Nanobioanalysis at Universities of Jilin Province, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, PR China
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
A facile and simple synthetic method of 3D CoFe2Se4/PCF via electrospinning for the first time. The CoFe2Se4/PCF shows high electrocatalytic activity to dihydroxybenzene isomers oxidation. Simultaneous detection of trace of hydroquinone, catechol and resorcinol. Obtained a wide linear range and low detection limits.
a r t i c l e i n f o
a b s t r a c t
Article history: Received 19 July 2019 Received in revised form 21 September 2019 Accepted 24 September 2019 Available online xxx
In this study, cobalt-iron selenides embedded in porous carbon nanofibers (CoFe2Se4/PCF), derived from Prussian blue analogues, was prepared as a novel phenolic sensor. The obtained CoFe2Se4/PCF nanocomposites show three-dimensional (3D) networks nanostructures that can supply a desirable conductive network to accelerate electron transfer and avoid the aggregation of CoFe2Se4 nanoparticles. Electrochemical detection of hydroquinone (HQ), catechol (CC) and resorcinol (RS), at CoFe2Se4/PCF modified glassy carbon electrode (GCE) were researched. The results show the obtained 3D CoFe2Se4/ PCF/GCE exhibits excellent electrochemical properties towards the simultaneous testing trace of HQ, CC and RS. The obtained electrode provides wide linear ranges of 0.5e200, 0.5e190 and 5e350 mM and low detection limit of 0.13, 0.15 and 1.36 mM for HQ, CC and RS, respectively. The as-prepared phenolic sensor displays satisfied selectivity and long-term storage stability. In addition, the constructed sensor can be used to determine HQ, CC and RS in actual samples. © 2019 Elsevier B.V. All rights reserved.
Keywords: Phenolic sensor CoFe2Se4/PCF nanocomposites Simultaneous testing Electrocatalysis
1. Introduction
* Corresponding author. ** Corresponding author. E-mail addresses: [email protected] (X. Bo), [email protected] (L. Guo).
Hydroquinone (HQ), catechol (CC) and resorcinol (RS), as three isomers of dihydroxybenzene, have been widely used in production of antioxidant, developer, medicines, pesticides, dye, cosmetics, tanning and photostabilizer [1e4]. However, dihydroxybenzene is poisonous and hard to degrade, menacing the environment and
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Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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crippling human and animal health [5,6]. It’s high time for researchers to develop an analytical technique that is sensitive and fast to detect dihydroxybenzene. So far, various analytical methods have been used to determine dihydroxybenzene isomers, including electrochemical methods [7], fluorescence [1], spectrophotometry [8], chemiluminescence [9], high performance liquid chromatography [10], capillary electrochromatography [11] and gas chromatography/mass spectrometry [12], Among these methods, electrochemical method has been attracted wide attention owing to its advantages of convenient operation, timesaving, low production cost and high sensitivity. Unfortunately, the dihydroxybenzene isomers, especially the oxidation and reduction of HQ and CC, are usually overlapped at ordinary electrode owing to their similar stereochemical structure. Therefore, it is almost impossible to detect them on bare GCE at the same time. In order to solve this issue, various materials are used to modify electrodes to detect HQ and CC, such as 3D sulfur/nitrogen co-doped graphene, Cu-MOF199/single-walled carbon nanotubes, multiwalled carbon nanotubes/polydopamine/gold nanoparticles composites and sodium citrate-derived 3D interconnected porous carbon modified GCEs [13e16]. Nevertheless, there are a few papers that report the sensitive and rapid detection of three dihydroxybenzene isomers. Therefore, the design of an advanced material with good catalytic activity to detect three dihydroxybenzene isomers is key to construct a sensitive phenolic biosensor. Metal selenides, have been received wide attention recently due to their excellent physical and electrochemical properties [17e19]. Among many metal selenides MSex (M ¼ Mo, Fe, Co, Mn Cu and Ni), FeSe2 and CoSe2 are attracting attention owning to their excellent electrical conductivity, substantial electrocatalytic activity and high specific capacitance, etc., [20,21]. In addition, catalysts with bimetallic active sites have better selectivity and catalytic activity in different chemical conversion processes than single metal catalysts,
which is due to the bonding among different metals could set up inherent polarity [22,23]. Therefore, CoFe2Se4 can be considered as the electrode material for an electrochemical sensor. However, semiconducting CoFe2Se4 has low density of available active sites and conductivity, limiting their use in electrocatalytic applications. Hence, developing more effective material as support to maximize exposure of the electrocatalytically active centre of CoFe2Se4 to substrates is necessary. Porous carbon fibers (PCF) with their ability to be woven into interconnected three-dimensional (3D) network structures have attracted attention, which can accelerate the transfer transport of materials and electrons [24]. PCFs have been widely used as supporting substrates in field of catalysis. Highly porous structure and high electrical conductivity make PCF an excellent supporting material for CoFe2Se4. Thus, we expect that CoFe2Se4/PCF nanocomposites will demonstrate excellent electrocatalytical properties because of their synergies. Herein, we developed a new electrocatalyst by selenizing the poly(acrylonitrile) (PAN) nanofibers embedded with nanocrystals of cobalt iron-based prussian blue analogues (CoFe-PBA) and CaCO3. After acid treatment, the CoFe2Se4 encapsulated into PCF (CoFe2Se4/PCF) were obtained. The specific steps are shown in Scheme 1. The results indicate that the 3D CoFe2Se4/PCF nanocomposites exhibit outstanding electrocatalytical properties while simultaneous testing of trace HQ, CC and RS. 2. Experimental 2.1. Reagents and instruments Hydroquinone (HQ), catechol (CC), and resorcinol (RS) were purchased from Tianjin, China. Bisphenol A, lysine, urea acid (UA) and ascorbic acid (AA) were obtained from Sinopharm Chemical
Scheme 1. Illustration of the preparation of CoFe2Se4/PCF.
Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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Reagent Co., Ltd. Polyacrylonitrile (PAN, average MW 80000), dimethylformamide (DMF, 99.5%), selenium powder, calcium carbonate (CaCO3, 99%), Nafion (5 wt %), hydrochloric acid (HCl, 37%), ethanol (C2H5OH, 99%) and potassium hydroxide (KOH, 99%) were obtained from Sigma-Aldrich. Cobalt chloride (CoCl26H2O, 99%), sodium citrate (Na3C6H5O72H2O, 98%) glucose and potassium ferricyanide (K3[Fe(CN)6], 99.5%) were purchased from Aladdin Reagent Company. All other chemicals were analytical grade and used without further purification. All electrochemical experiments were carried out on a CHI 660C Electrochemical Workstation (CH Instruments, China) in a conventional three-electrode configuration. The modified glassy carbon electrode (GCE, 3 mm diameter), platinum electrode and Ag/AgCl (in saturated KCl solution) electrode work as the working electrode, the counter electrode and the reference electrode, respectively. All potentials in this paper involved versus Ag/AgCl. X-ray diffraction (XRD) patterns were acquired with an X-ray D/max-2200vpc (Rigaku Corporation, Japan) instrument operated at 40 kV and 20 mA using Cu Ka radiation (l ¼ 0.1541 nm). SEM images and EDX were acquired on a HITACHI SU8010 SEM. Nitrogen adsorptionedesorption isotherms were measured on an ASAP 2020 Micromeritics (USA) at 77 K. The BET method was utilized to calculate the specific surface area. The pore size distribution plot was derived from the adsorption branch by using the BJH model. 2.2. Synthesis of CoFe-PBA CoFe-PBA was synthesized as reported previously with some modification [25]. The details are listed in Supporting information. 2.3. Synthesis of PAN/CoFe-PBA/CaCO3 nanofibers and CoFe2Se4/PCF CoFe-PBA (0.8 g), polyacrylonitrile (PAN, 0.8 g, average MW 80000) and CaCO3 (0.4 g) were dispersed in N, N-dimethylformamide (DMF). Subsequently, the solution was stirred overnight and then poured into a syringe. Afterward, a high pressure of 13 kV was applied and the collector was placed 15 cm from the spinneret for obtaining PAN/CoFe-PBA/CaCO3 fiber. Furthermore, the nanofibers were dried at 60 C for 24 h in vacuum condition, which is benefit for forming stable network structures after the remove of solvent residues. Subsequently, the PAN/CoFe-PBA/CaCO3 nanofibers and selenium powder (1 g) were put into a tube furnace. In addition, the distance between the selenium powder and the nanofibers was 0.5 cm. Then the tube furnace was place at the downstream side. Firstly, the PAN/CoFe-PBA/CaCO3 nanofibers were pre-treated in nitrogen at 270 C at a heating rate of 1 C min1 for 1 h. Then, they were pyrolyzed at 500 C at a heating rate of 5 C min1 for 2 h. Afterward, the obtained nanofibers were removed CaCO3 by immersing into 1.0 M HCl. After washing and drying for 24 h at 60 C in vacuum, the final CoFe2Se4/PCF-2 sample was then obtained. In addition, CoFe2Se4/PCF-1 and CoFe2Se4/PCF-3 samples were prepared through putting 0.4 mg and 1.6 mg of CoFe-PBA into the spinning solution, respectively. In comparison, CoFe2Se4 catalyst was synthesized by pyrolyzing directly CoFe-PBA at the same condition. In addition, PCF catalyst was also prepared by calcining PAN/CaCO3 under identical condition and further acid treatment. 2.4. Preparation of the modified electrodes To begin with, GCE was polished by alumina powders prior to modification, then cleaned thoroughly with deionized water. The clean GCE was dried in air. Then, 3 mg of catalyst was dispersed in
3
1 mL Nafion (0.5 wt %) and treated by sonicate for 0.5 h to form the catalyst suspension. Next, 5 mL of the suspension was casted on the surface of GCE and dried in air. 3. Results and discussion 3.1. Characterization of CoFe2Se4/PCF-2 composites The phase of CoFe-PBA is investigated by XRD in Fig. S1. The sharp diffraction peaks confirm CoFe-PBA has been prepared successfully [26]. Fig. 1A displays the XRD patterns of CoFe2Se4/PCF-2. The four characteristic peaks at 33.47, 44.90 , 51.52 and 70.48 correspond to the (112), (114), (020) and (404) planes of the CoFe2Se4 (JCPDS No. 65e2337), respectively [27]. In addition, a broad 25 peak at CoFe2Se4/PCF-2 sample can be assigned to (002) plane of graphitic carbon, suggesting that CoFe2Se4/PCF-2 catalyst has been successfully synthesized. As shown in Fig. 1B, CoFe-PBA has cubic shape and relatively uniform size of 250e500 nm. After calcination, the agglomeration of CoFe-PBA takes place obviously (Fig. 1C). The morphology of CoFe-PBA, CaCO3 and PAN after electrospinning (PAN/CoFe-PBA/CaCO3 nanofibers) are presented in Fig. 1D. Compared to PAN nanofibers (Fig. S2A), there are obvious protuberances on the surface of PAN/CoFe-PBA/CaCO3 nanofibers due to successful introduction of CoFe-PBA and CaCO3. In particular, a plurality of nanofibers is winded to construct a three-dimensional network. Fig. 1E exhibits the morphologies of PAN/CoFe-PBA/CaCO3 after the pyrolysis treatment. The surface of the selenized fibers of PAN/CoFe-PBA/CaCO3 have two different sizes of protrusions, corresponding to CaCO3 (Fig. S2B) and CoFe-PBA, respectively. After acid treatment (Fig. 1F), CoFe2Se4/PCF catalyst with porous and 3D net-like structures was obtained. EDX spectrum has been applied to further reveal the chemical composition of the CoFe2Se4/PCF-2. Fig. 1G displays the existence of C, N, O, Co, Fe and Se in CoFe2Se4/ PCF-2. The N2 adsorption-desorption isotherms, BET specific surface area and pore volume of CoFe2Se4/PCF-2 and CoFe2Se4 are presented in Fig. S3 and Table S1, the data indicating PCF can increase the BET specific surface area and pore volume of CoFe2Se4, which is advantageous to higher electrocatalytic activity by offering more active sites. 3.2. Electrocatalytic oxidation of HQ, CC and RS at CoFe2Se4/PCF-2 To explore the electrocatalytic activity of CoFe2Se4/PCF to HQ, CC and RS oxidation, cyclic voltammetry (CV) was employed. Fig. 2(AC) shows the CVs at bare GCE, PCF/GCE, CoFe2Se4/GCE and CoFe2Se4/PCF-2/GCE in 0.1 M PBS (pH 7.0) containing 0.2 mM HQ, CC and RS, respectively. Fig. 2A displays a pair of broad redox peaks with small peak currents when bare GCE is used to detect HQ, which is similar to that of CoFe2Se4/GCE. When PCF/GCE is used to detect HQ, the redox peaks are not evident although the background currents increase obviously. In contrast, CoFe2Se4/PCF-2/ GCE reveals a pair of significant redox peaks. It can be seen that the current of oxidation peak for the CoFe2Se4/PCF-2/GCE (Ipa ¼ 11.78 mA) is about 5.8 times higher than that of CoFe2Se4/GCE (Ipa ¼ 2.04 mA). Therefore, CoFe2Se4/PCF-2/GCE exhibits much better electrocatalytic activity than GCE, PCF/GCE and CoFe2Se4/GCE to HQ. Fig. 2B displays the redox peaks of CC on different electrodes, which are similar to that of HQ. Nevertheless, only one oxidation peak of RS on the various electrodes is gained (Fig. 2C), indicating the oxidation of RS is a completely irreversible. Fig. 2D reveals the CVs at bare GCE, PCF/GCE, CoFe2Se4/GCE and CoFe2Se4/PCF-2/GCE in 0.1 M PBS (pH 7.0) mixture solution containing 0.2 mM HQ, CC and RS. The oxidation and reduction peaks of HQ and CC are overlapped on bare GCE. Furthermore, the peak of HQ, CC and RS is hardly observed on PCF/GCE. Hence, it is infeasibility to detect
Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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Fig. 1. (A) XRD pattern of CoFe2Se4/PCF. SEM images of CoFe-PBA (B), CoFe2Se4 (C), PAN/CoFe-PBA/CaCO3 nanofibers (D), CoFe2Se4/PCF precursor (E) and CoFe2Se4/PCF sample (F). (G) EDX spectrum of CoFe2Se4/PCF.
simultaneously HQ, CC and RS at bare GCE and PCF/GCE. For CoFe2Se4/GCE, the peak currents are small though the redox peaks of HQ and CC and the peak of oxidation of RS are provided. As expected, the two pairs of redox peaks at 0.102 V, 0.048 V (HQ) and 0.212 V, 0.172 V (CC) and one oxidation peak at 0.589 V (RS) are found in the CVs for CoFe2Se4/PCF-2/GCE. The two pairs of redox peak currents of HQ and CC and the oxidation peak current of RS at CoFe2Se4/PCF-2/GCE are higher than those of CoFe2Se4/GCE. From the results above, the simultaneous detection of HQ, CC and RS can be gained on CoFe2Se4/PCF-2/GCE. The excellent performance may be explained the following reasons. To begin with, 3D interconnected structure PCF with continuous path is advantageous to accelerate electron transfer. Furthermore, PCF with large surface area is benefit for allowing the facile accessibility of the electrode/ electrolyte interface, leading to a promotion of electrochemical performance to HQ, CC and RS. Finally, PCF could avoid the collapse and aggregation of CoFe-PBA, which is favorable for improving electrocatalytic activity. In addition, the influence of the content of CoFe2Se4 is researched (Fig. 2E). It is shown that CoFe2Se4/PCF-2/ GCE has the best electrocatalytic effect. Therefore, CoFe2Se4/PCF-2/ GCE was selected for subsequent experiments.
3.3. Influence of scan rate and pH Fig. S4 depicts the peak currents of HQ and CC and the peak current of RS have a good linear relationship with the scan rate. Those results indicate that the electrochemical oxidation of HQ, CC
and RS are adsorption-controlled electrochemical processes on the CoFe2Se4/PCF-2/GCE [28]. Afterward, Fig. 3A provides the effect of solution pH (4.0e8.0) on the response of HQ, CC and RS at CoFe2Se4/PCF-2/GCE via differential pulse voltammetry (DPV). The oxidation peak potential of HQ, CC and RS shifts negatively with the increase of pH, revealing that the oxidations of HQ, CC and RS involves protons. Fig. 3B depicts the linear relationship between the oxidation peak potential of HQ, CC and RS. These three lines are nearly parallel, indicating the peak potential difference is a constant. According to the well-known Nernst equation:
dEp 2:303mRT ¼ nF dpH where T is kelvin temperature, R is the universal gas constant, F is the Faraday constant (96485 C mol1), m and n are the number of protons and electrons, respectively. From the slope of dEp/dpH, the value of m/n could be counted to be 1.015, 1.071 and 1.071 to the oxidation process of HQ, CT and RS, respectively. Those results indicate the number of electrons participating is the same as the number of protons of reaction, which is comply with the twoelectron and two-proton process reported previously [13]. Moreover, the oxidation peak currents of HQ, CC and RS reach the largest at the pH 7.0 (Fig. S5). Hence, pH 7.0 is the best pH value for the later study.
Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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Fig. 2. (A)The CVs at bare GCE, PCF/GCE, CoFe2Se4/GCE and CoFe2Se4/PCF-2/GCE in 0.1 M PBS (pH 7.0) containing of 0.2 mM of HQ (A), 0.2 mM of CC (B), 0.2 mM of RS (C) and a mixture of three dihydroxybenzene isomers (each of 0.2 mM) (D). (E) CVs of a mixture of three dihydroxybenzene isomers (each of 0.2 mM) at CoFe2Se4/PCF-x/GCE electrode. Scan rate: 10 mV s-1.
Fig. 3. (A) DPV curves at CoFe2Se4/PCF-2/GCE containing 0.15 mM HQ, 0.15 mM CC and 0.2 mM RS in the pH range from 4.0 to 8.0. (B) The relationship between pH and the oxidation peak potentials of HQ, CC and RS.
3.4. Selective analysis of HQ, CC and RS Quantitative analysis of HQ, CC and RS on CoFe2Se4/PCF-2/GCE are performed by DPV since DPV possesses higher sensitivity than CV. In the case where the concentrations of the other two substances are constant, Fig. 4A, Fig. 4B and Fig. 4C depict the selective detection of HQ, CC and RS. As demonstrated in Fig. 4A and B, HQ is selectively detected in the existence of 50 mM CC and 20 mM RS with obvious response at 0.1 V. The peak currents of HQ increase linearly with the level of HQ while there is no obvious
variation for the currents response of CT and RS are no obvious vary. Inset a displays the liner regression equation and liner range is 0.5e200 mM for HQ. The detection limit (LOD) of HQ is calculated to be 0.13 mM based on a signal-to-noise factor of 3 (S/ N ¼ 3). Similarly, the peak currents of oxidation for CC and RS increase linearly with their concentrations as demonstrated in Fig. 4B, inset b, Fig. 4C and inset c, respectively. The linear ranges for CC and RS are 0.5e190 mM and 5e350 mM with LOD of 0.15 mM and 1.36 mM, respectively. Table 1 displays the comparison of CoFe2Se4/PCF-2/GCE with other catalysts for simultaneous
Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
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Fig. 4. (A) DPV of different concentrations of HQ (0.5e200 mM) in the presence of 50 mM CC and 20 mM RS, (B) CC (0.5e190 mM) in the presence of each 50 mM HQ and RS, (C) RS (5e350 mM) in the presence of each 50 mM HQ and CC in 0.1 M PBS (pH 7.0). The corresponding calibration plots between HQ (inset a), CC (inset b) and RS (inset c) concentration and current signal of oxidation peak for CoFe2Se4/PCF-2/GCE, respectively.
Table 1 Comparison of the performances of the simultaneous determination of HQ, CC and RS sensors. Electrode
AuPdNF/rGO/GCE P-rGO/GCE Graphene-CS/GCE UiO-66/MC-3/GCE Cu3(btc)2/CS-ERGO/GCE AgNP/MWCNT/GCE MIL-101(Cr)-rGO-2-CPE aGO1/SPCE CoFe2Se4/PCF-2/GCE
Linear range (mM)
Detection Limit (mM)
Ref.
HQ
CC
RS
HQ
CC
RS
1.6e100 5e90 1e300 0.5e5.0, 5.0e100 5.0e400 2.5e260 10e1400 1e312 0.5e200
2.5e100 5e120 2e400 0.4e100 2.0e200 20e260 4e1000 1e350 0.5e190
2.0e100 5e90 1e550 30e100, 100e400 1.0e200 e e e 5e350
0.5 0.08 0.75 0.056 0.44 0.16 4.1 0.27 0.13
0.8 0.18 0.75 0.072 0.41 0.2 0.66 0.182 0.15
0.7 2.62 0.75 3.51 0.33 e e e 1.36
detection of HQ, CC and RS. The results show the prepared phenolic sensor exhibits a wide linear range and low detection limit, which make the property of the CoFe2Se4/PCF-2/GCE sensor comparable and even better than the reported recently. 3.5. Simultaneous analysis of HQ, CC and RS The excellent property of CoFe2Se4/PCF-2/GCE for HQ, CC and RS detection is also demonstrated via the simultaneously increasing the concentration of three isomers. Three well-separated and distinct oxidation peaks for HQ, CC and RS are represented in Fig. 5A. As shown in Fig. 5BeD, the linear ranges of HQ, CC and RS are 0.5e180 mМ, 1e160 mМ and 10e120 mМ and with LOD of 0.53, 0.84 and 2.62 mM, respectively.
[3] [29] [6] [30] [31] [32] [33] [34] This work
the CoFe2Se4/PCF-2/GCE exhibits satisfactory long-term storage stability.
3.7. Diluted lake water analysis To assess feasibility of CoFe2Se4/PCF-2/GCE, the diluted lake water samples were tested. No target analytes are found in diluted lake water samples. The standard addition method was used to determine HQ, CC and RS. The results are provided in Table 2. The values of recoveries are 95.3e102.0%, 96.9e102.8% and 95.2e100.8% for HQ, CT and RS, respectively. Therefore, the proposed sensor could be used to determine HQ, CC and RS in diluted lake water analysis.
3.6. The selectivity and stability investigated
4. Conclusion
In addition, the selectivity and stability of CoFe2Se4/PCF-2/GCE are also studied. Fig. S6A shows the current responses of CoFe2Se4/ PCF-2 to 0.1 mM HQ, 0.1 mM bisphenol A, 0.1 mM glucose, 0.1 mM lysine, 0.1 mM urea acid (UA) and 0.1 mM ascorbic acid (AA). There is no obvious current change when the interfering substances are added. The selectivity to CC and RS at CoFe2Se4/PCF-2/GCE as shown in Fig. S6B and Fig. S6C, respectively. The results indicating that CoFe2Se4/PCF-2/GCE displays high selectivity at their certain active potentials for HQ, CC and RS. Moreover, the stability of CoFe2Se4/PCF-2/GCE is also investigated. Fig. S6D illustrates that the current signals are lower than 7.13%, 8.34%, 12.18% of the original for HQ, CC and RS after 15 days, respectively, suggesting that
In conclusion, we prepared a novel phenolic sensor based on CoFe2Se4/PCF nanocomposite to determine of trace HQ, CC and RS simultaneously. The as-prepared sensor exhibits excellent electrochemical properties towards the simultaneous testing trace of HQ, CC and RS. The obtained electrode provides wide linear ranges of 0.5e200 mM, 0.5e190 mM and 5e350 mM and low detection limit of 0.13 mM, 0.15 mM and 1.36 mM for HQ, CC and RS, respectively. At the meantime, the obtained sensor provids good antiinterference property and outstanding stability. Moreover, this work opens up the possibility of using three-dimensional PCF loaded metal selenides as a sensing platform for the detection of HQ, CC and RS.
Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057
D. Yin et al. / Analytica Chimica Acta xxx (xxxx) xxx
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Fig. 5. (A) DPV of different concentrations of HQ (0.5e180 mM), CC (1e160 mM) and RS (10e120 mM) in 0.1 M PBS (pH 7.0). The corresponding calibration plots between HQ (B), CC (C) and RS (D) concentration and current signal of oxidation peak for CoFe2Se4/PCF-2/GCE, respectively.
Table 2 Determination of dihydroxybenzene isomers in lake water samples at the CoFe2Se4/ PCF-2/GCE (n ¼ 3). Sample
1 2 3
Added (mM)
Found (mM)
Recovery (%)
HQ
CC
RS
HQ
CC
RS
HQ
CC
RS
30 60 90
30 60 90
60 120 180
30.6 57.2 88.1
28.1 61.7 87.2
57.5 118.6 181.4
102.0 95.3 97.9
97.0 102.8 96.9
95.2 98.8 100.8
Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments Financial support from National Natural Science Foundation of China (21575021) is highly appreciated.
Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.aca.2019.09.057.
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Please cite this article as: D. Yin et al., Cobalt-iron selenides embedded in porous carbon nanofibers for simultaneous electrochemical detection of trace of hydroquinone, catechol and resorcinol, Analytica Chimica Acta, https://doi.org/10.1016/j.aca.2019.09.057